Plastigels containing hydroxy fatty acid soaps



'June 4, 1957 T. c PATTON l-:rAL 2,794,791 PLASTIGE'LS CONTAININCHYDRoxY FATTY'ACID soAPs Filed April 3, 1953 Expt. lo

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o 4s se |44 |92 24o as 336 Hours INVENTORS Temple Chapman. PattonB,"Freaerick Milton Hall AGENT Y United Sttes PLSTIGELS CNTAING HYERSXYFATE( ACE SAPS Temple Chapman Patton and Frederick Milton Hall,Westlield, N. 3., assignors to The Bal-:er Castor @il Company, JerseyCity, N. 3., a corporation of New -iersey Application April 3, 1953,Serial No. 345,754

11 Claims. (Cl, 269-23) This invention pertains to the preparation ofimproved vinyl chloride resin plastigels. It is particularly directed tothe use of irnproved gelling agents which yield plastigels havingexceptional heat stability.

It has been known in the prior art to use the soaps of non-hydroxy fattyacids as gelling agents for vinyl chloride resin plastigels. Such soapsin low proportions give gels which are undesirably soft at thetemperatures, namely, 30G-400 F., required for fusion of the plastigelsto enable them to attain their maximum strength, and are also so soft atroom temperature (prior to fusion) as to have limited practical utility.Other gelling agents have been used, including organic derivatives ofmontmorillonite. Plastigels formed with these latter agents have thedisadvantage of discoloring at the temperatures required for fusion.

It is an object of this invention to produce vinyl chloride resinplastigels having satisfactory heat stability at fusion temperatures. itis a further object of this invention to provide gelling agents whichwhen used in low proportions yield plastigels having a suitably firmconsistency for molding operations prior to fusion. Other objects willbe apparent from the following description of the invention.

lt has novv been found that these objects can be attained by the use, asgelling agents, of alkaline earth metal soaps of hydroxy fatty acidshaving at least l1 carbon atoms.

soaps give outstanding results in providing a satisfactorily' hard gelstructure, and in stabilizing the composition so as to preventdiscoloration during fusion.

Among the hydroxy fatty acids which lare suitable for use in the form Yof :their soaps, a particularly preferred group is those having 18carbon atoms, such as ricinoleic acid, 12-hydroxyY stearic acid,9,10-dihydroxystearic acid, dihydroxy oleic Other suitable hydroxy Aacid, sativic acid, and the like. acids for use in forming the gellingagents of this inven- Y to be that comprising tricresyl phosphate,dioctyl phthal-V 2,794,79l Patented June 4, 1957 ice Chemical Cal);Vinylite QYNV (Carbide and Carbon' Chemicals Co); Exon 654 (FirestoneTire and Rubber Co); and Marvinol VR-lO (Naugatuck Chemical Division ofUnited States Rubber Co.). The gelling agents of this invention can beused Ywith any of the usual plasticizers, llers, or stabilizers in theformulation and production of improved plastigels. Y

A particularly suitable plastigel composition comprises the followingingredients in the stated parts by weight:

Vinyl chloride resin 90-110A Plasticizer 50-110 Filler 40-125-Stabilizer Y Y A l7 Gelling agent of this inventicn 1-1 5 If desired,the amounts of one or more of these ingredients may be varied from thosestated, but compensating changes in the amounts of the other ingredientsare usually required. Pigments can be added as desired.

Usual mixing techniques can be used for the thorough blending of theseveral ingredients. It is feasible to mix all of the ingredients in oneoperation in a pony or dough mixer with a sigma blade. If desired, thegelling agent can be added toward the end of the mixing operation.Somewhat more ecient mixing and thickening action are obtained if thegelling agent is dispersed in a portion of the plasticer on a 3rollmill, or at elevated temperatures and cooled, and then added to the`other compounds in the mixer. Similarly, it is desirable to dispersethe pigmentsin a portion of the plasticizer before they are combinedwith the other ingredients in the mixer. The mixing procedure need notbe a lengthy one; mixing times factory. Y Y Y i As indicated, any of theusualplasticizerrs may be used satisfactorily inthe compositions of thisinvention. A particularly suitable group of plasticizers has been foundate, and linear polyesters formed by the esterication of glycols anddi-carboxylic acids. There is some tendency for such plasticizers toimparta surface-tack to therplastihydroxy fatty acids. The gellingagents of-fthisinvention` Y. aresuitably'used 'inert v.analmlrltranging, from about 1 tQ' ii' about'lS weight percent, basedron theamount of the vinyli Q f w' j, Y Y Y, Y j agents of this inventlon, aswell as with prior art gellmg The vinyl chloride resins which aresuitable for use in60 preparing plastigels include polyvinyl chloride,'vinyl" Lchlorlde lresinfl chloride-vinyl acetate copolymers, vinylchloride-vinylidene chloride copolymers, as well as copolymers of vinylchloride with vinyl Ypropionate, vinyl butyrate, Vvinyl gel systems; andthis tack can be overcome byV using a Yco-plasticizer, notably, theacetylated esters of ricinoleic acid, such as methyl acetoxyricinoleate, butyl acetoxy ricinoleate, Z-methoxyethyl acetoxyricinolea-te, and the like. Y

Experimental data on plasti'gels formed with the gelling agents, arepresented in the accompanyin'gtable. These plastigels were prepared byintroducing all of the ingredieach case was twenty minutes, this beingsufficient to ResmO l Y Y Di-octyl Phthalate...V

obtain complete mA 'ix'in g. In somein'stances, as indicated in thetable, diiculty was experienced with the plastigel composition stickingto the sigma blade, as well as to the mixer Walls. It will be noted thatthe compositions which did so stick contained a soap of a non-hydroxyfatty acid or a non-alkaline earth metal soap of a hydroxy fatty acid asthe gelling agent.

The consistency of the plastigels, as freshly prepared and after agingat room temperature for up to 168 hours, Was determined by means of aPrecision penetrometer; a 1h50Q weight was used, and the readings weretaken after seconds. In addition to the summary of the penetrometer datapresented in the table, some of the penetrom'eter results are presentedin the'accompanying gure. In general, ka desirable range for consistencyof l5 the plastigels is fromk about 150 to about 20D (these beingVpenetrometer readingsrobtained as indicated above). It is to bernortedthatcompostions containing thegelling agents of this invention (Expts.1-4 in the ligure) have consistencies in'this range. Soapftype gellingagentsnOt covered by this vinvention form plasti'gelsY (penetrometerreadings greater'than 290; Exp'ts. 10 Iand lv6 in Ithe figure), whicharefmuch too soft for practical consideration.

YSimple shaped pieces of the plastigels were fused for 1Q minutes at`350" lj". to determine their heat and dimensional stability. TheVgellingl agents of this invention gave superior results on this test,the plastigels containing barium and calcium ricinoleate beingoutstanding. Thebest previously available gelling agent, namely, Ben*tone 34, did not pass this test, asv ity darkened to an un- 3Q Inthetable, resin A is polyvinyl chloride; resin B is Vinyl Vchloridevinylacetate copolynier;A and resin C is vinyl chloride-vinylidenn Y.chloridecopolymer. The phthals acid and ricinoleicacid es ters are used asV theplasticizers,

while the filler used is a treated Whiting. Bentone 34 is anorganophilic montmorillonite. BVS, as a 50:50 blend with the indicatedplasticizer, is used as the stabilizer throughout, and -is a modifiedbarium ricinoleate. It

will be noted that this compound was used in sutlicient 40 1'v Theadvantageous results obtained with the gellingr agents of this inventionare shown by the data reported in the table for the followingexperiments:

Experiment N o. Gelling Agent Barium rieinoleate.

Calcium ricinoleatc.

Magnesium ricinoleate.

strontium ricinoleate.

Calcium 3, 12-d1hydroxy palmitate. Calcium hydroxy-undecanoato.

Comparative data for other gelling agents are listed under the followingexperiments:

Experiment No. Gelling Agent Sodium palmitate.

Aluminum ricinoleate. Aluminum laurate.

Aluminum octoate.

Barium stearate.

Calcium oleate.

Magnesium undecanoate. Zircomum hydroxy-nndecanoate. Bentone 34.

It can readily he seen from the experimental data that `the gellingagents of this invention constitute a substantial advance over the priorart, as their use enables the production of completely satisfactoryplastigels. Prior art soap-type gelling agents form plastigels which areso soft as to have limited utility. And the prior art gelling agentwhich forms satisfactorily stiff gels is not suciently stable `at therequired fusion temperature. Both of these drawbacks lare overcome bythe instant gelling agents.-

The plastigels of this invention may be molded, calendered, spread,embossed, extruded, etc. at room temperature and under moderatepressures. After the plastigels have been formed into desired shapes,they do not need any special support prior to or4 during the fusionstep. Typical applications for the plast'igels include oor tile,continuous sheeting, wire coatings, cloth coating, tubing, moldedobiects containing inserts, orthopedic appliances, caulking compounds,gaskets, potting compounds and the like. l

Numerous other modifications and variations in the invention describedherein will be apparent to those skilled in the art, and are Within thespirit and scope of the appended claims.

Table Expt.No 1A 2 j 3 Resin A Resin B f Butyl acetoxy vioinnlpatoMethyl acetoxy ricinoleata -l 2-methoxyethyl acetoxy ric Whiting NoDal'k- Dal'k- Darkemng. erung. ening. enlng. ening. ening.

Expt. N 11 l2 13 14 Resin A 100 100 100 Resin B- 100 Resin C- Di-octylPhthalate 30 30 30 Butyl acetoxy ricinoleate 30 Methyl aeetoxyricinoleate 30 2-methoxy ethyl acetoxy rin Bentone 'i4 30 Whltlng 50 5050 BVS-P-i 5 5 BVS-Flexrcin 62- Mg. rio.-P4 Ca ric.-P4. Ca rid-Flexricn62-. Ba st.-P-4 10 Al octoate-P-d Ca oleate-P-4 Mg und-P4- sticks Toosoft Sticking to Mill.- Penetrometer..

Fusion at 350 F o1 KI No d ark- No dark- N o darkemng. emng.

sticks Too soft sticks Too soft sticks Too soit sticks Too soft O. K. O.K.

Darkens O. K. Poor gel structure Darkens Too soit What is claimed is:

1. A plastigel composition comprising a fluid dispersion of a vinylchloride-containing resin in a liquid plasticizer, and, in suiiicientamount to effect gelation of said dispersion, from 1 to l5 weightpercent, based on the amount of said resin, of an alkaline earth salt ofa hydroxy fattyl acid containing at least 1l carbon atoms, saidcomposition, after being aged at room temperature for about 300 hours,having a Precision penetrometer reading (150 gm. weight at 15 seconds)of from about 150 to about 200.

2. The composition of claim 1, in which said vinyl chloride-containingresin is polyvinyl chloride.

3. The composition of claim 1, in which said vinyl chloride-containingresin is a vinyl chloride-vinyl acetate copolymer.

4. The composition of claim 1, in which said vinyl chloride-containingresin is a vinyl chloride-vinylidene chloride copolymer.

5. The composition of claim 1, in which said hydroxy fatty acid haseighteen carbon atoms.

6. The composition of claim 1, in which said salt is calciumricinoleate.

7. The composition of claim 1, in which said salt is barium ricinoleate.

8. A plastigel composition comprising a uid dispersion of 90-110 partsby Weight of a Vinyl chloride-containing resin in 50-110 parts by Weightof a liquid plasticizer, and, as a gelling agent for said dispersion,1-15 parts by weight of an alkaline earth salt of a hydroxy fatty acidcontaining at least 11 carbon atoms, said composition, after being agedat room temperature for about 300 hours, having a Precision penetrometerreading (150 gm. Weight at 15 seconds) of from about 150 to about 200.

9. A plastigel composition comprising a fluid dispersion of -11() partsby Weight of a vinyl chloride-containing resin, 40-125 parts by Weightof a ller, and 1-7 parts by Weight of a stabilizer in 50-110 parts byWeight of a liquid plasticizer, and, as a gelling agent for saiddispersion, 1-15 parts by Weight of an alkaline earth salt of a hydroxyfatty acid containing at least 11 carbon atoms, said-composition, afterbeing aged at room temperature for about 300 hours, having a Precisionpenetrometer reading gm. weight at 15 seconds) of from about 150 toabout 200.

10. The composition of claim 9, in which said plasticizer is a blend ofdioctyl phthalate and an acetylated ester of ricinoleic acid.

11. The composition of claim 9, in Which said plasticizer is a blend ofdioctyl phthalate and methyl acetoxy ricinoleate.

References Cited in the le of this patent Rubber Age, article byPartridge et al., vol. 67, No. 5, August 1950, pages 553-560.

Modern Plastics, article by Parker et al., vol. 30, No. 6, February1953, pages 129, 130, 132, 134 and 218.

1. A PLASTIGEL COMPOSITION COMPRISING A FLUID DISPERSION OF A VINYLCHLORIDE-CONTAINING RESIN IN A LIQUILD PLASTICIZER, AND, IN SUFFICIENTAMOUNT TO EFFECT GELATION OF SAID DISPERSION, FROM 1 TO 15 WEIGHTPERCENT, BASED ON THE AMOUNT OF SAID RESIN, OF AN ALKLINE EARTH SALT OFA HYDROXY FATTY ACID CONTAINING AT LEAST 11 CARBON ATOMS, SAIDCOMPOSITION, AFTER BEING AGED AT ROOM TEMPERATUE FOR ABOUT 300 HOURS,HAVING A PRECISION PENETROMETER READIGN (150 GM. WEIGHT AT 15 SECONDS)OF FROM ABOUT 150 TO ABOUT 200.